Acetal and ketal phosphonates



United States Patent Ofice 3,206,474 Patented Sept. 14, 1965 3,206,474ACETAL AND KETAL PHGSPHONATES Ingenuin Hechenbleikner and Kenneth R.Molt, Cincinnati, Ohio, assignors to Carlisle Chemical Works, Inc.,Reading, Ohio, a corporation of Ohio N Drawing. Filed Dec. 20, 1962,Ser. No. 245,976 7 Claims. (Cl. 260-340-7) This application is acontinuation-in-part of application 214,508, filed 3,096,345.

The present invention relates to novel phosphonates. It is an ob ect ofthe present invention to prepare phos- Another object is to preparenovel heterocyclic acetal and ketal phosphonates.

0 Rz Rl where R is hydrogen alkyl, aryl, haloaryl or nitroaryl, R ishydrogen, alkyl aryl, haloaryl or nitroaryl; or

is an alicyclic, i.e., a cycloalkyl group, alkyl or aryl, R is hydrogenor alkyl, R is hydrogen or alkyl, R is hydrogen, or lower alkyl, e.g.,methyl or ethyl, v is 0 or an integer, e.g., from 1 to 100, n is aninteger between 1 and 10, m is 1 or 2;

R is hydrogen,

O CH2 where R is alkyl, alkenyl or aralkyl and R and R are as definedabove August 3, 1962, now US. Patent No. 1

where R is alkyl, alkenyl aryl, haloaryl or aralkyl and R R and R are asdefined above where R R R R R are as defined above and x is an integerof at least 1, e.g., from 1 to 100.

There are also included phosphonates of diacetals and ketals or hexitolssuch as sorbitol and mannitol. Typical of such materials are compoundshaving the formula where R R and R are as defined above.

In Formula V no attempt has been made to show the atoms on theasymmetric carof the acetal and ketal groups as there are two suchgroups position in the molecule.

The compounds of the present invention are useful as water dispersiblewetting and suspending agents. They can also be employed as fireretardants for cellulose, cellulose esters, e.g. cellulose acetate, polyolefin resins, e.g. polyethylene and polypropylene.

A particular important use for the acetals and ketals of the presentinvention is to hydrolyze them to give hydroxyl containing phosphonates.Such hydroxyl containing phosphonates have the following formulae whereR is as defined above, R is alkyl, alkenyl, aralkyl, aryl, haloaryl or Rand R as Ra R3 R4 (CHzHWAOHzh-QCQ OH OH where R R R R v, n and m are asdefined above;

OCH;

il/ RioP 0 CH2 CHgOH VII where R is as defined above;

where R is as defined above.

The hydrolyzed phosphonates, i.e. the compounds of Formulae VI, VII, andVIII, have the uses set forth supra and in addition are useful forpreparing polyurethanes organic isocyanates, e.g. toluenediisoisocyanate averaging by reaction with cyanate and PAPI(polyphenylene about 3 units in the polymer). The polyurethanes can beprepared as foams or as elastomers. The presence of the phosphonategroup renders the polyurethane flame resistant. The phosphonate need byused only as a portion of the polyols employed. Thus, the use of 20% ofa polyhydroxyl containing phosphonate according to the present and 80%of another polyol, e.g. glycerine propylene oxide adduct molecularweight 3000 or polypropylene glycol 2025 will give a polyurethane withimproved flame resistance.

' The novel compounds of Formulae I through V of the present inventionare prepared by Arbuzov rearrangement of the corresponding phosphiteprepared according to the parent application. The entire disclosure ofthe parent application is hereby incorporated by reference.

Thus, there is employed an alkyl halide, alkenyl halide, aralkyl halide,halohydrin or epihalohydrin with a phosphite of the parent applicationthat is isomeric with a phosphonate of Formulae I through V above. Theiodides and bromides are preferred although there can also be employedthe chlorides. The halides can be employed in catalytic amounts, e.g.0.5-5 mol percent based on the phosphite to be rearranged. If thehydrocarbon group of the halide is the same as one of the esterifyinggroups of the phosphite, then no impurities are introduced into thephosphonate product. By employing a large amount of the halide, e.g. 80mol percent, or preferably 100 mol percent or more, based on thephosphite employed in the Arbuzov reaction, then the product is one inwhich one of the esterifying groups on the phosphorus atom is removedand the phosphorus atom is directly attached to the hydrocarbon,hydroxyhydrocarbon or epoxyhydrocarbon group of the halide employed.When one of the sterifying groups of the phosphite is aryl or haloaryl,sufiicient alkyl halide or the like must be used to replace the aryl orhaloaryl group since aryl halides do not normally take part in theArbuzov reaction. The Arbuzov reaction is usually carried out atelevated temperatures, e.g. 120200 C. at atmospheric, subatmospheric orsuperatmospheric pressure. The halide remaining after the reaction cannormally be removed by distillation.

Among the halides which are employed in the Arbuzov reaction are methylbromide, methyl iodide, ethyl bromide, ethyl iodide, n-propyl iodide,isopropyl iodide, amyl bromide, amyl chloride, amyl iodide, butylbromide, hexyl iodide, octyl bromide, octyl iodide, decyl bromide, decyliodide, dodecyl iodide, octadecyl bromide, octadecyl iodide, allylbromide, allyl iodide, allyl chloride, methallyl iodide, crotyl bromide,vinyl bromide, oleyl bromide, oleyl iodide, benzyl chloride, benzylbromide, benzyl iodide, ododecylbenzyl chloride, p dodecylbenzylchloride, mdodecylbenzyl chloride p dodecylbenzyl bromide,epichlorhydrin, epibromohydrin, 'epiiodohydrin, ethylene chlorhydrin,ethylene bromohydrin, ethylene iodohydrin, propylene chlorhydrin,propylene bromohydrin.

The compounds of Formulae VI through VIII are prepared by hydrolysis ofthe compounds of Formulae I, II, and V. The hydrolysis is caried outwith the aid of water, preferably with heating, e.g. up to 100 C. Thereaction mixture is usually slightly acidic due to the startingphosphonate. After hydrolysis is completed, an alkaline material, e.g.sodium hydroxide, sodium carbonate, sodium bicarbonate or potassiumhydroxide is added to neutralize the product.

Illustrative examples of starting phosphites (which can be prepared inthe manner set forth in the parent application) to prepare thephosphonates of Formula I are phenyl bis (4-(2-methyl-2-ethyl-1,3-dioxacyclopentyl) methyl) phosphitedipheny1-4-(Z-methyl-Z-ethyl- 1,3-dloxacyclopentyl) methyl phosphite;methyl bis (4-(2-methy1-Z=e thy1-1,3-dioxacyclopentyl) methyl)phosphite;

dimethyl 4- (2-methyl-2-ethyl- 1 ,3-dioxacyclopentyl) methyl phosphite;

ethyl bis (4- (2-methyl-2-ethyl- 1 ,3-dioxacyclopentyl) methyl)phosphite, tris (4 2-methyl-2-ethyll ,3 dioxacyclopentyl) methyl)phosphite;

decyl bis(4-(2-methyl-2-ethyl-1,3-dioxacyclopentyl) methyl) phosphite",octadecyl bis (4- Z-methyl-Z-ethyl- 1,3-dioxacyclopentyl) methyl)phosphite;

dioctadecyl 4-(2-methyl-2-ethyl-1,3-dioxacyclopentyl) methyl phosphite;

oleyl bis (4(2-methyl-2-ethyl-1,3-dioxacyclopentyl) methyl) phosphite;

benzyl-bis (4- (2-methyl-2-ethyl-1,3-dioxacyclopentyl) methyl)phosphite;

p-dodecylb enzyl-bis (4- 2-methyl-2-ethyl-1 ,3 -dioxacy clopentyl)methyl) phosphite;

cyclohexyl-bis- (4- (2-methyl-2-ethyl-l ,3-dioxacyclopentyl) methyl)phosphite;

tris 5 2,5 -dirnethyl-2-ethyl- 1 3-dioxacy clohexyl) methyl) phosphite;

ethyl bis(5-(2,5-dimethyl-2-ethyl-1,3-dioxacyclohexyl) methyl)phosphite;

dimethyl-S (2,5 -dimethyl-2-ethyl- 1 ,3 -dioxacyclohexyl) methylphosphite;

lauryl bis- 5 (2,5 -dimethyl-2-ethyl-1 ,3-dioxacyclohexy1) methyl)phosphite;

allyl bis'( 5 (2, 5 -dimethyl-2-ethyl- 1 3 -dioxacyclohexyl) methyl)phosphite;

cyclopentyl-bis (5 (2,5 -dimethyl-2-ethyl- 1 ,3-dioxacyclohexyl) methyl)phosphite;

dibutyl-S (2,2,5 -trirnethyl- 1 ,3-dioxacyclohexyl) methyl phosphite;

butyl bis(5-(2,2,S-trimethyl-1,3-dioxacyclohexyl) methyl) phosphite;

tris 5 2,2, S-trimethyl- 1 ,3-dioxacy clohexyl) methyl) phosphite;

propyl bis 5 (2,2,5 -trimethyl- 1 ,3-dioxacyclohexyl) methyl) phosphite;

tris(4- (2,2-dimethyl-1,S-dioxacyclopentyl) methyl) phosphite;

methyl bis (4-(2,2-dimethyl-1,3-dioxacyclopentyl) methyl) phosphite;

octadecyl bis(4-(2,2-dimethyl-1,3-dioxacyclopentyl) methyl) phosphite;

isobutyl bis (4-(2,2-dimethyl-1,3-dioxacyclopentyl) methyl) phosphite;

ethyl bis (4- 1,3-dioxacyclopentyl) methyl) phosphite;

tris (4-( 1,3-dioxacyclopentyl) methyl) phosphite;

dioctadecyl (4- 1 ,3-dioxacyclopentyl) methyl) phosphite;

tris(4-(2-methyl-1, 3 -dioxacyclopentyl methyl) pho sphite,

ethyl bis(4-(2-methyl-1,3-dioxacyclopentyl) methyl) phosphite;

tris(4- (2-ethyl-1,3-dioxacyclopentyl) methyl) phosphite;

methyl bis(4-(2-ethyl-1,3-dioxacyclopentyl) methyl) phosphite;

diolleyl 4-(2-ethyl-1,3-dioxacyclopentyl) methyl phosp ite;

tris (4- (2-propyl-1 ,3-dioxacyclopentyl) methyl) phosphite;

benzyl bis(4- (2-propyl-1,3-dioxacyclopentyl)methyl) phosphite;

decyl bis(4-(2-propyl-1,3-dioxacyclopentyl) methyl) phosphite;

ethyl bis(4-(Z-heptadecyl-l,3-dioxacycl0pentyl)methyl) phosphite;

methyl bis(4- (2-heptadecenyl-1,3-dioxacyclopentyl) methyl) phosphite;

tris (4- (2-viny1- 1 ,3-dioxacyclopentyl methyl) phosphite;

amyl bis (4- (2-vinyl-1 ,3-dioxacyclopentyl methyl) phosphite;

dodecyl bis(4-(2-phenyl-1,3-dioxacyclopentyl)methyl) phosphite;

octyl bis (4-(2-p-methylphenyl-1,3-dioxacyclopentyl) methyl) phosphite;

octadecyl bis(4-(2-o-chlorophenyl-1,3-dioxacyclopentyl) methyl)phosphite;

bis (dimethoxyphosphaoxydecoxy) methane; 1, l-bis(diethoxyphosphaoxybutoxy) ethane; 1, l-bis dipropoxyphosphaoxydecoxy)ethane; 1,1-bis(dioleyloxyphosphaoxybutoxy) propane;1,l-bis(dipentoxyphosphaoxydecoxy) propane;1,1-bis(dioleyloxyphosphaoxypentoxy) propane;1,l-bis(didecoxyphosphaoxybutoxy) butane; 1,1-bis(dicyclohexoxyphosphaoxybutoxy) -2-methylpropane;1,1-bis(dimethoxyphosphaoxybutoxy) dodecane; 1,1-bis(diisopropoxyphosphaoxydecoxy) dodecane; 1,1-bis(dimethoxyphosphaoxybutoxy) octadecane;1,l-bis(diethoxyphosphaoxydecoxy) octadecane;bis(dibutoxyphosphaoxybutoxy) (phenyl) methane; 1,1-bis(di-dodecoxyphosphaoxybutoxy) propene-2;1,1-bis(diethoxyphosphosphaoxydecoxy) propene-Z;1,l-bis(dipropoxyphosphaoxybutoxy) butene-Z; 1,1-bis(dimethoxyphosphaoxybutoxy) octadecene-9;1,1-bis(dihexoxyphosphaoxybutoxy) (cyclohexyl) methane;bis(dioctoxyphosphaoxybutoxy) (phenyl) methane;bis(dimethoxyphosphaoxypentoxy) (p-methylphenyl) methane;bis(dioctadecoxyphosphaoxybutoxy) (o-chlorophenyl) methane;bis(dimethoxyphosphaoxybutoxy) (m-nitrophenyl) methane; 2,2-bis(didecoxyphosphaoxybutoxy) pentane; 2,2-bis(dimethoxyphosphaoxypentoxy)pentane; 3,3-bis (dimethoxyphosphaoxybutoxy) pentane;3,3-bis(dipentoxyphosphaoxydecoxy) pentane; 2,2-bis(dimethoxyphosphaoxypentoxy) hexane; 3,3-bis (diethoxyphosphaoxybutoxy)hexane; 2,2-bis (dimethoxyphosphaoxybutoxy) 3,3-dimethylbutane; 4,4-bis(dipropoxyphosphaoxyhexoxy) heptane;6,6-bis(dihexadecoxyphosphaoxybutoxy) undecane;18,18-bis(dimethoxyphosphaoxybutoxy) pentatricontane 1, 1-bis(dibutoxyphosphaoxybutoxy) cyclohex'ane; 1,1-bis(dimethoxyphosphaoxybutoxy) cyclopentane; bis(dioctoxyphosphaoxybutoxy)(diphenyl) methane; 1, l-bis(dimethoxyphosphaoxyoct-oxy)-1-phenylethane;1,l-bis(dirnethoxyphosphaoxybutoxy)-1phenyl propane; bis(dimethoxyphosphaoxyethoxyethoxy) methane; 1,1-bis(dipropoxyphosphaoxyethoxyethoxy) ethane1,l-bis(didecoxyphosphaoxyethoxyethoxy) butane;2,2-bis(diethoxyphosphaoxyethoxyethoxy) propane; 2,2-bis(dimethoxyphosphaoxyethoxyethoxy) butane;

1,1-bis (dimethoxyphospha-2-oxypropoxypropoxy) ethane;2,2-bis(dibutoxyphospha-Z'-oxypropoxypropoxy) propane;2,2-bis(dipentoxyphoSpha-2'-oxypropoxypropoxy) butane;2,2-bis(dimethoxyphosphaoxypolyethoxy) propane (where the polyethoxygroup has a molecular weight of 2000); 2,2-bis(dioctoxyphosphaoxypolypropoxy) butane (Where the polypropoxy group as amolecular Weight of 1000); 1,1-bis (diethoxyphosphaoxybutoxybutoxy)cyclohexane; bis dimethoxyphosphaoxyethoxyethoxyethoxy) (phenyl)methane.

Illustrative of phosphonates of the present invention within FormulaeIII and IV are 2,2-bis[(niethoxy) (methanephosphonobutoxy)] propane u In CHaP-O (3411 (I) O C4H9O P-CHa CHaO CH OCH3 2,2-bis( (methoxy) 2'hydroxyethanephosphonobutoxy) propane; 2,2-bis((methoxy)2'-hydroxypropanephosphonobutxoy) propane; 2,2-bis((methoxy)epoxypropanephosphonobutoxy) propane; 2,2-bis((decoxy) decane- 1,1-bis(decoxy) 2,2-bis((butoxy) butanephosphonobutoxy) butane; 2,2-

bis((ethoxy) ethanephosphonopentoxy) butane; 2,2-bis- ((methoxy) methanephosphonodecoxy) butane; 2,2-bis- ((octoxy) octanephosphonoeicosanoxy)butane; 2,2-bis- ((ethoxy) ethanephosphonohexoxy) butane;bis((octadecoxy) octadecanephosphono-butoxy) methane; bis((dodecyloxy)dodecanephosphonopentoxy) methane; bis- ((methoxy)methanephosphonodecoxy) methane; 1,1- bis ((ethoxy)ethanephosphonobutoxy) ethane; 1,1-bis- ((propoxy)propanephosphonodecoxy) ethane; 1,1-bis- ((oleyloxy) A-octadecenephosphonobutoxy) propane; 1,1- bis((pentoxy)pentanephosphonodecoxy) propane; 1,1- bis( (oleyloxy) A-octadecenephosphonopentoxy) propane;

decanephosphonobutoxy) butane; 1,1- bis( (cyclohexoxy)cyclohexanephosphono butoxy 2 me'thylpropane; 1,1-bis((methoxy)methanephosphon'c butoxy) dodecane; 1,1-bis((isopropoxy)isopropanephosphonodecoxy) dodecane; 1,1-bis((methoxy)methanephosphonobutoxy) octadecane; 1,1-bis((ethoxy)ethanephosphonodecoxy) octadecane; bis((butoxy) butanephosphonobutoxy)(phenyl) methane; 1,1-bis((dodec0xy) dodecanephosphonobutoxy) propene-Z;1,1-bis((ethoxy) ethanephosphonodecoxy) propene-2; 1,1-bis((propoxy)propanephosphonobutoxy) butene-2; 1,1-bis((methoxy)methanephosphonobutoxy) octadecene-9; 1,1,-bis((hexoxy)hexanephosphonobutoxy) (cyclohexyl) methane; bis((octoxy)octanephosphonobutoxy) (phenyl) methane; bis((methoxy)methanephosphonopentoxy) (p-methylphenyl) methane; bis((octadecoxy)octadecanephosphonobutoxy) (o-chlorophenyl) methane; bis((methoxy)methanephosphonobutoxy) (m-nitrophenyl) methane; 2,2- bis((decoxy)decanephosphonobutoxy) pentane; 2,2-bis- ((methoxy)methanephosphonopentoxy) pentane; 3,3- bis((meth0xy)methanephosphonobutoxy) pentane; 3,3- bis((pentoxy)pentanephosphonodecoxy) pentane; 2,2- bis((methoxy)methanephosphonopentoxy) hexane; 3,3- bis((ethoxy)ethanephosphonobutoxy) hexane; 2,2-bis- ((methoxy)m-ethanephosphonobutoxy) 3,3-dimethyl-butane; 4,4-bis((propoxy)propanephosphonoxhexoxy) heptane; 6,6-bis((hexadecoxy)hexadecanephosphonobutoxy) undecane; 18,18-bis((methoxy)methanephosphonobutoxy) pentatricontane; 1,1-bis((butoxy)butanephosphonobutoxy) cyclohexane; 1,1-bis((methoxy)methanephosphonobutoxy) cyclopentane; bis((octoxy)octanephosphonobutoxy) (diphenyl) methane; 1,1-his((methoxy)methanephosphonooctoxy) 1 phenylethane; 1,1 bis- ((methoxy)methanephosphonobutoxy)-l-phenylpropane; bis((methoxy)methanephosphonoethoxyethoxy) methane; 1,1-bis((propoxy)propanephosphonoethoxyethoxy) ethane; 1,1-bis((decoxy)decanephosphonoethoxyethoxy) butane; 2,2-bis((ethoxy)ethanephosphonoethoxyethoxy) propane; 2,2-bis((methoxy)methanephosphonoethoxyethoxy) butane; 1,1-bis((methoxy)methanephosphonoisopropoxyisopropoxy) ethane; 2,2-bis((butoxy)butanephosphonoisopropoxyisopropoxy) propane; 2,2-bis((pentoxy)pentanephosphonoisopropoxyisopropoxy) butane; 2,2-bis((methoxy)methanephosphonopolyethoxy) propane (where the polyethoxy group has amolecular weight of 2,000); 2,2-bis((octoxy) octanephosphonopolypropoxy)butane (where the polypropoxy group has a molecular weight of 1000);1,1-bis((ethoxy) ethanephosphonobutoxybutoxy) cyclohexane; bis((methoxy)methanephosphonoethoxyethoxyethoxy) (phenyl) methane.

Illustrative examples of starting phosphites (which can be prepared inthe manner set forth in the parent application) useful for preparing thephosphonates of the Formula V are 5,6-monophenyl phosphite ester of1,3,2,4-

' mono decyl phosphite ester or 1,3,2,4-dieyc1ohexlyidene sorbitol;5,6-mono methyl phosphite ester of 1,3,2,4-'tli'-' methylene sorbitol;5,6-mono methyl phosphite ester of 1,3,2,4-di isobutylidene sorbitol;3,4-mon amyl phosphite ester of 1,2,5,6-di benzylidene mannitol;3,4-mono decyl phosphite ester of 152,5,6-di ethylidene mannitol;5,6-mono cyclohexyl phosphite ester of 1,3,2,4-'di n-butylidenesorbitol.

Illustrative of phosphonates of the present invention within Formula Vare 5,6-methonephosphonate ester of 1,3 ,2,4-diisopropylidene sorbitolCH 0 CH2 C O CH l CH3 "-0 CH /CH3 e H O CH; /O( JH CHaP 0 OCH;

5,5 ,2-hydroxyethanephosphonate ester of 1,3,2,4-

diisopropylidene sorbitol; 4,5,2-hydroxypropanephosphonate ester of1,3,2,4-

diisopropylidene sorbitol; 5,6-epoxypropane-phosphonate ester of'1,3,2,4-

diisopropylidene sorbitol; 5,6-phenylmethanephosphonate ester of1,3,2,4-

diisopropylidene sorbitol; 5,6-decanephosphonate ester of 1,3,2,4-

diisopropylidene sorbitol; 5,6-octadecanephosphonate ester of l,3,2,4-

diisopropylidene sorbitol; 5,6-A -octadecenephosphonate ester of1,3,2,4-

diisopropylidene sorbitol; 5,6-cyclohexanephosphonate ester of 1,3,2,4-

diisopropylidene sorbitol; 5,6-butanephosphonate ester of l,3,2,4-

diethylidene sorbitol; 5,6-ethanephosphonate ester of 1,3,2,4-

dibenzylidene sorbitol; 3,4-propenephosphonate ester of 1,2,5,6-

diisopropylidene mannitol; 3,4-hexadecanephosph0nate ester of 1,2,5,6-

diisopropylidene mannitol; 5,6-decanephosph0nate ester of 1,3,2,4-

dicyclohexylidene sorbitol; 5,6-methaneph0sphonate ester of 1,3,2,4-

di-methylene sorbitol; 5,6-methanephosphonate ester of 1,3,2,4-

di-isobutylidene sorbitol; 3,4-pentanephosphonate ester of 1,2,5 ,6:

di benzylidene mannitol; 3,4-decane phosphonate ester of 1,2,5 ,6-

diethylidene mannitol; 1;5,6-cyclohexanephosphonatc 16! Of 1,32,

di 'n-butylidene sorbitol,

16 Illustrative of phosphonates of the present invention Within FormulaVI are phenyl 2,3-dihydroxypropyl methanephosphonatebis(2,3-dihydroxypropyl) methane phosphonate',

bis(2,3-dihydroxypropyl) 2-hydroxyethanephosphonate;

bis(2,3-dihydr0xypropyl) 2-hydroxypropanephosphonate;

I methyl 2,3-dihydroxypropyl methanephosphonate;

bis(2,3-dihydroxypropyl) ethanephosphonate; bis(2,3-dihydroxypropyl)2,3-dihydroxypropanephosphonate; bis(2,3-dihydroxypropyl)decanephosphonate; bis(2,3-dihydroxypropyl) octadecanephosphonate;octadecyl 2,3-dihydroxypropyl octadeeanephosphonate; bis2,3-dihydroxypropyl) M-octadecanephosphonate; bis(2,3-dihydroxypropyl)phenylmethanephosphonate; bis(2,3-dihydroxypropyl)p-dodecylphenylmethanephosphonate; bis(2,3-dihydroxypropyl)cyclohexanephosphonate; bis 3-methyl-2,4-dihydroxybutyl) 3-methyl 2,4-

dihydroxybutanephosphonate bis(3-methyl-2,4-dihydroxybuty1)ethanephosphonate; methyl 3-methyl-2,4-dihydroxybutyl methylphosphonateO OCH;

C I-IaP C Ha OCHQ$H2HOH2OH 0 H bis 3-methyl-2,4-dihydroxybutyl)dodecanephosphonate; bis 3-methyl-2,4-dihydr0xybuty1)propenephosphonate; bis 3-methyl-2,4-dihydroxybutyl)cyclopentanephosphonate; butyl 3-methyl-2,4-dihydroxybutylbutanephosphonate; bis 3-methyl-2,4-dihydroxybutyl) butanephosphonate;bis 3-methyl-2,4-dihydroxybutyl) propanephosphonate;bis(2,3-dihydroxypropyl) isobutanephosphonate;

it [CHQCHCHZP (0 CHQCHOHCHBOHM Ha oleyl 2,3-dihydroxypropane-A-0ctadecenephosphonate; bis(2,3-dihydroxypropyl) pentanephosphonate;bis(2,3-dihydroxypropyl) dodecanephosphonate; bis(2,3-dihydroxypr0pyl)octanephosphonate; amyl 2,3-dihydroxypropyl pentanephosphonate;bis(2,3-dihydroxypropyl) butanephosphonate;bis(2,3-dihydroxypropoxypropyl ethanephosphonate (H) CH3 [CgH5P-(O471161120 OH2CHO1 CH2OI )2] bis(2,3-dihydroxypropoxy polyethoxymethanephosphonate having 30 ethoxy groups if [CHsP-(O(CH2CH20)30GH2CHOHOH2OH)2] bis(5 ,6 dihydroxyhexyl) 5,6dihydroxyhexanephosphonate [HO CHzCHoHCiHoP (O C4H9CH0HCHOH 1bis(5,6-dihydroxyhexyl) decanephosphonate; ethyl 5,6-dihydroxyhexylethanephosphonate; bis(5,6-dihydroxyhexyl) methanephosphonate; bis (5,6-dihydr0XyheXyl) hexanephosphonate; bis(5,6-dihydroxyhexyl)phenylmethanephosphonate;

17 bi s(5,6- dihydroxyhexyl) heptanephosphonate; bis(2,3-dihydroxybutyl)2,3-dihydroxybutanephosphonate; bis(2,3-dihydroxybutyl)propanephosphonate; bis(2,3-dihydroxyamyl) butanephosphonate;bis(2-methyl-2,3-dihydroxybutyl) methanephosphonate;bis(2,2-di(hydroxymethyl) propyl decylphosphonate (H CH 1011 211 CH JJCH2OH HgOH bis 2,2-di(hydroxymethyl) butyl butanephosphonate 'amyl2,2-di(hydroxymethyl) butylpentanephosphonate 0 0-0511, omni CHzOH SOCH-COH CH CHzOH bis(2,2-di(hydroxymethyl) amyl)ethanephosphonate;

'bis(2,2-di(hydroxymethyl) monadecyl) propenephos- Illustrative ofphosphonates of the present invention within Formula VII are5,5-dihydroxymethyl-1,3-dioxa-2- methanephosphonocyclohexane 1 011,011

0 l \CHQOH |)/0 CH: [C H3 1 o 0111 5 ,S-di hydroxymethyl) 1,3-'dioxa-2-2'-hydroxyethane) phosphonocyclohexane; 5,5 -di hydroxymethyl1,3-dioxa-2- 2'-hydroxypropane) phosphonocyclohexane; 5 ,S-dihydroxymethyl) 1,3-dioxa-2-octadecanephosphonocyclohexane; 5 ,5-di(hydroxymethyl) -1,3-dioxa-2-propenephosphonocyclohexane CH OH C OOBz\CHZOH 5,5-di(hydroxymethyl) 1,3-dioxa-2-A-octadecenephosphonocyclohexane;5,5-di(hydroxymethyl)-1,3-dioxa-2-phenylmethanephosphonocyclohexane; -5,5 di (hydroxymethyl) l 3 dioxa-2-pdodecylphenylthanephosphonocyclohexane;5,5-di(hydroxymethy1)-1,3-dioxa-Z-decanephosphonocyclohexane;5,5-di(hydroxymethyl)-1,3-dioXa-2-cyclohexanephosphonocyclohexane;5,5-di(hydroxymethyl)1,3-dioxa-2-butanephosphonocyclohexane;

5 ,5 -di( hydroxymethyl)-1,3-dioxa-2-pentanephosphonocyclohexane;

5 ,5 -di hydroxymethyl)-1,3-dioxa-2-ethanephosphonocyclohexane;

5,5-di(hydroxymethyl)-1,3-dioxa-2-(1-methyl) ethanephosphonocyclohexane;

5 ,5 -di hydroxymethyl) 1,3 -dioXa-2-dodecanephosphonocyclohexane;

5 ,5 -di (hydroxymethyl)-1,3-dioxa-2-octanephosphonocyclohexane;

5,5-di(hydroxymethyl)-1,3-dioxa-2-hexadecanephosphonocyclohexane;

5 ,5 -di( hydroxymethyl)-l,3-dioXa-2-hexanephosphonocyclohexane;

5 ,5 -di( hydroxymethyl)-1,3-dioxa-2-propanephosphonocyclohexane.

Illustrative of phosphonates of the present invention within FormulaVIII are 5,6-methanephosphonate ester of sorbitol; 5,6-(2'-hydroxy)ethane phosphonate ester of sorbitol; 5,6-(2-hydroxy) propanephosphonateester of sorbitol; 5,6-pheny1methanephosphonate ester of so rbitol;5,6-decaneph0sphonate ester of sorbitol; 5,6-octadecanephosphonate esterof sorbitol; 5,6-A -octadecenephosphonate ester of sorbitol;5,6-butanephosphonate ester of sorbitol; 5,6-ethanephosphonate ester ofsorbitol; 3,4-propenephosphonate ester of mannitol;3,4-hexadecanephosphonate ester of mannitol; 3,4-pentanephosphonateester of mannitol; 3,4-decanephosphonate ester of maunitol.

Unless otherwise indicated, all parts and percentages are by weight.

Example 1 8 moles of acetone, 2 moles of trimethylolethane, 400 grams 0was collected in a Dean and Stark trap. Heating was continued until thetheoretical amount of Water had been removed. The product was2,2,5-tn'methyl-S-methylol- 1,3-dioxacyclohexane, a colorless viscousliquid, yield 283 grams (88.2% of theory) B.P. 84-88" C./0.8 mm.,showing significant infrared absorptions at 2.78 (OH) and 9.22 (cyclicether) microns.

Example 2 8 moles of methyl ethyl ketone, 4 moles of glycerine, 400grams of hexane and 10 grams of p-toluenesulfonic acid were refluxed inthe manner described in Example 1. From the reaction mixture wasisolated 2-methyl-2-ethyl- S-methylol-1,3-dioxacyclopentane, a colorlessliquid boiling at 63-67 C./0.3 mm., yield 485 grams (82.8% of theory),hydroxy value 382.7 (theory 383) having the formula H H0OH2E-|7H2 0 0 oa C2 s The product is also called 2-methyl-2-ethyl-4-methylol-1,3-dioxacyclopentane.

Example 3 2.1 moles of cyclohexanone, 2.0 moles of glycerine, grams oftoluene and 2 grams of 50% aqueous sulfuric acid were refluxed for 3hours into a Dean and Stark trap during which time the theoreticalamount of water was collected. The reaction mixture was neutralized with2 grams of sodium carbonate, filtered and the solvent removed in vacuo.The product which was recovered by distillation was 2,2pentamethylene-S- hydroxymethyl-1,3-dioxacyclopentane, a colorlessliquid,

B.P. 98103 C./0.6 mm., 11 1.4780, showing strong infrared absorption at2.78 (OH) and 9.05 (ether) microns; yield 305 grams (88.5% of theory).

Example 4 6.0 moles of methyl ethyl ketone, 3.0 moles of 1,2,6-hexanetriol, 400 grams of hexane and 10 grams of ptoluenesulfonic acidwere refluxed for 8 hours while collecting the Water formed by thereaction in a Dean and Stark trap. From the reaction mixture wasisolated 490 grams (86.7% yield) of 2-methyl-2-ethyl-5 (4-hydroxybutyl)1,3 dioxacyclopentane, a colorless liquid B.P. 106-1l0 C./ 0.6 mm.,hydroxyl value 294.5 (theory 298).

Example 5 1.0 mole of trimethyl phosphite and 2.0 moles of 2- methyl 2ethyl 5(4 hydroxybutyl) 1,3 d-ioxacyclopentane. The ketal of Example 4were heated with 1 gram of sodium methoxide for 1 hour at 80 to 140 C.(pot temperature) while allowing methanol to distill from the reactionmixture through a packed column. After vacuum stripping, the product wasfiltered to give 430 grams (98.5% of theory) of methyl bis[(4-(2-methyl-2-ethyl-1,3-dioxacyclopentyl)butyl] phosphite a colorless liquid havingthe formula CH OP OCH OH:CH CHqCH-?H 2 CH: CzHb Example 6 The procedureof Example 5 was repeated but utilizing 2.0 moles of2,2-pentamethylene-5-hydroxymethyl-1,3- dioxacyclopentane (the ketal ofExample 3) in place of the ketal of Example 4. The product was methylbis- (3 (1,4 diox-aspiro (5,5) .decyl)methyl) phosphite, a colorlessviscous liquid obtained in a yield of 96.3% and having the formulaExample 7 I The procedure of Example 5 was repeated but utilizing 2.0moles of 2,2;5-trimethyl 5 methylol-l, 3-dioxacyclohexane (the ketal ofExample 1) in place of the ketal of Example 4. The product was methylbis- (5- (2,2,5-trimethyl-1,3-dioxacyclohexyl)methyl) phosphite.

Example 8 The procedure of Example 5 was repeated but utilizing 2.0moles of 2-methyl-2-ethyl-S-methylol-1,3-dioxacyclopentane (the ketal ofExample 2) in place of the ketal of Example 4 and using 1 mole oftrioctadecyl phosphite in place of the trimethyl phosphite. The productwas octadecyl bis(4-(2-methyl-2-ethyl-1,3-dioxacyclopentyl) methyl)phosphite.

Example 9 200 grams of the methyl bis(4-(2-methyl-2-ethyl-1,3-dioxacycloperrtyDbutyl) phosphite (t-he ketal phosphite prepared inExample 5) was heated for 7 hours at 140- 150 C. with one gram of ethyliodide as a catalyst. The conversion to phosphonate was followed byperiodic sampling and titration with 0.1 N iodine in benzene during theheating period. All of the phosphite was converted after the 7 hours ofheating. After vacuum stripping, there was obtained as the product in ayield of 99.4% bis(4-(2-methyl-2-ethyl-1,3-dioxacyclopentyl)- 20 butyl)methanephosphonate as a colorless liquid having the structure:

There was a slight impurity ofbis(4-(2-methyl-2-ethyll,S-dioxacyclopentyl)butyl) ethane-phosphonate.In .an-

other run by using methyl iodide rather than ethyl iodide as thecataylst the impurity was completely eliminated.

Example 10 Example 11 The procedure of Example 10 was repeated replacingthe ketal phosphite of Example 6 with 200 grams of methyl bis(5 (2,5dimethyl-Z-ethyl-1,3-dioxacyclohexyl) methyl) phosphite and using 1 gramof methyl iodide as the catalyst. The product was bis(5(2,5 dimethyl-Z-ethyl-1,3-dioxacyclohexyl)methyl) methanephosphonate.

Example 12 The procedure of Example 9 was repeated replacing the ketalphosphite of Example 5 with 200 grams of octadecyl bis (4-(2-methyl-2-ethyl-1;3-dioxacyelopentyl) methyl) phosphite and using 1gram of octadecyl bromide as the catalyst. The product wasbis(4-(2-methyl- 2-ethyl 1,3 dioxacyclopentyl) methyl)octadecanephosphonate.

Example 13 The procedure of Example 9 was repeated replacing the ketalphosphite of Example 5 by 2-methoxy-9-methyl-9-ethyl-1,3,8,10-tetraoxa-2-phosphaspiro (5,5) undecane and using 1 gramof methyl iodide as the catalyst. The product was2-(methane)-9-methyl-9-ethyl-1,3,8,10-tetraoxa-2-phosphonospiro (5,5)undecane.

Example 14 The procedure of Example 9 was repeated replacing the ketalphosphite of Example 5 by 200 grams of 2,2- bis-(dimethoxyphosphabutoxy)propane and using 1 gram of methyl iodide as the catalyst. The productwas 2,2- bis( (methoxy) methanephosphonobutoxy) propane.

Example 15 The procedure of Example 9 was repeated replacing the ketalphosphite of Example 5 by 200 grams of the 5 ,6-rnonodecyl phosphiteester of 1, 3,2,4-diisopropylidene sorbitol and using 1 gram of decyliodide as the catalyst. The product was 5,6-decanephosphonate ester of1,3,2,4- diisopropylidene sorbitol.

100 grams of his(4-(2-methyl-2-ethyl-1,3-d-ioxacyclopentyl)butyl)methanephosphonate (the ketal phosphonate of Example 9) was heating for30 minutes at 80 C. with an equal Weight of Water. The pH of the mixturewas between 2 and 4 due to a small residual acidity of the ketalphosphonate. By the end of the heating period, the reaction mixture washomogeneous due to hydrolysis of the ketal groups. There was no changein acidity indicating no hydrolysis of the phosphonate to phosphonicacid. The reaction mixture was cooled, neutralized to a pH of 7 withsodium hydroxide and the water was removed in vacuo. The filteredproduct was bis(5,6-dihydroxyhexy1) methanephosphonate, a colorlessviscous liquid obtained in quantitative yield, and having a hydroxylvalue of 694 (theory 683) and having the formula II CH P(OCHzCH CHCHgCHCHgOHh H Example 17 The procedure of Example 16 was repeatedreplacing the ketal phosphonate of Example 9 by 100 grams of bis(3(1,4-dioxaspiro (5,5) decyl) methyl) methanephosphonate (the ketalphosp'honate of Example 10). The product Was bis(2,3-dihydroxypropyl)methanephosphonate, a colorless syrup obtained in a yield of 98.7% andhaving the formula I CH 1(OCH2CHCH:OH)

Example 18 The procedure of Example 16 was repeated replacing the ketalphosphonate of Example 9 by 100 grams of 2- (methane)-9-methyl-9-ethyl1,3,8,10 tetraoxa-Z-phosphono spiro (5,5) undecane. The product was5,5-dihydroxymethyl 1,3 dioxa-Z-methanephosphonocyclohexane.

Example 19 The procedure of Example 16 was repeated replacing the ketalphosphonate of Example 9 by 100 grams of 5,6-decanephosphonate ester of1,3,2,4-diisopropylidene sorbitol. The product was the5,6-decanephosphonate ester of sorbitol.

What is claimed is:

1. A phosphonate having the formula if R1IIO R9 R50 where R; is selectedfrom the group consisting of alkyl, alkenyl, benzyl, alkylbenzyl, epoxylower alkyl, hydroxy lower alkyl, and R R is selected from the groupconsisting of alkyl, al-

22 kenyl, phenyl, benzyl, alkybenzyl, alkyl phenyl, naphthyl, halophenyland R R9 is Ra Ra R{\ R5 2 B )v( 2)n I o R2 R1 R and R are selected fromthe group consisting of hydrogen, alkyl, alkenyl, phenyl, alkyl phenyl,halophenyl and nitrophenyl, individually, and

R2 together form a cycloalkyl atoms;

R is selected from the group consisting of hydrogen,

alkyl, phenyl and alkyl phenyl;

R and R are selected from the group consisting of hydrogen and alkyl;

R is selected from the and lower alkyl;

v is selected from the an integer;

n is an integer selected 1 and 4;

m is an integer between 1 and 2 inclusive,

2. Bis (4 1,3-dioxacyclopentyl) methyl alkanephosphonate having up to 2alkyl groups attached to the number 2 carbon atom of thedioxacyclopentane ring.

3. Bis(3 (1,4 dioxaspiro(5,5)decyl)methyl)alkanering of 5 to 6 carbongroup consisting of hydrogen group consisting of zero and from the groupconsisting of F phosphonate,

4. Bis(4-( 1,3 dioxacyclopentyl)butyl)alkanephosphonate having up to 2alkyl groups attached to the number 2 carbon atom of thedioxacyclopentane ring.

5. Bis(3 (1,4-dioxaspiro(5,5)decyl)butyl)alkanephosphonate.

6. Bis(S-(S-lower alkyl-1,3-dioxacyclohexyl)methyl)alkanephosphatehaving up to 2 alkyl groups attached to the number 2 carbon atom of the1,3-dioxacyclohexane ring.

7. Bis(3-(1,5 dioxaspiro(6,6)undecyllbutyl)alkanephosphonate.

References Cited by the Examiner UNITED STATES PATENTS WALTER A.MODANCE, Primary Examiner. NICHOLAS S. RIZZO, Examiner.

1. A PHOSPHONATE HAVING THE FORMULA